DE69816083T2 - Process for accelerating the reaction of ozone and wastewater using a catalyst - Google Patents

Description

technical area

The present invention relates to a method of raising the reaction rate of ozone in the treatment of water by injecting ozone into the water to remove harmful Materials, smelling materials and colored materials in this.

technical background

Dealt with in previous years people deal a lot with the environment. In particular, water was the has an intimate relationship with their way of life, a matter of primary importance.

Harmful materials, such as organic ones Substances, ammonia and the like, and materials that smell and Colors can cause are in secondary Waste water treatment water, secondary night pollution treatment water, industrial waste water, tap water, water from small supply systems, Water from a single tap, water for commercial use, Water from a wastewater recycling system and wastewater from fish farms and culture ponds contain.

Therefore, it is necessary to make water strong to treat. Various water treatment processes have been investigated. In particular, the contamination of rivers with organic substances is Phenol types of great Importance. Of concern are nonylphenols or nonylphenol isomers, the as estrogen that causes problems as an environmental hormone.

The nonylphenol isomers are generated while in Wetting agents and the like contained chemical substances decomposed in rivers become. The organic substances of the phenol type have a benzene ring on and can not easily decomposed by heating and the like. By the addition of chlorine will make decomposition possible. However, if the organic Phenol-type substances are decomposed with added chlorine, become undesirable Chlorides formed.

As one as described above Treatment of water is using a water treatment process known from ozone. To remove harmful materials, smelling Materials and colored materials through oxidative decomposition and this method is widely used for pasteurization.

For the purpose of increasing the oxidative decomposition rate more harmful Materials in water with ozone, i.e. H. the treatment rate of the water, is a method of adding a wetting agent, which causes contact between polluted water and ozone, as in the unexamined Japanese patent publication No. 52-8650.

As is well known, the oxidation reaction of ozone in water is based on the reaction with direct contact of an ozone molecule and the hydroxyl radical (OH •) and the hydroperoxy radical (HO ₂ •), which are generated by the self-decomposition of ozone. In particular, the hydroperoxy radical (HO •) has a higher oxidizing power. The increase in hydroperoxy radicals leads to a highly efficient reaction.

The following procedures to speed up the The above reaction is known: the pH of the water to be treated will be raised; Hydrogen peroxides are added; Ultraviolet radiation will let act; Radiation is applied; ultrasonic waves are applied; Catalysts such as metal ions, metal oxides and Like., are used; and the like

A known method also exists for the treatment of polluted water with ozone in the presence of a Phenol, from benzoic acid and dodecylbenzenesulfonic acid as a catalyst. For example, such a method is shown in the untested Japanese Patent publication No. 06-23377.

In the procedures described above however, ozone is relatively expensive and the oxidative decomposition rate of ozone low. Therefore, water treatment with high efficiency only with difficulty by introducing water to be treated large in a reaction tank Dimensions and injection of ozone realized.

According to the procedure by adding of a wetting agent disclosed in Japanese Unexamined Patent Publication No. 52-8650 the response is increased the area of the reaction sites accelerated. If large quantities of organic materials present in the water to be treated are the wetting agent through the organic materials in the water are adsorbed so that the foaming capacity is reduced is. If the amount of wetting agent is increased, the decreased Foaming power too compensate, a very large amount of foam is generated, which likely to cause processing problems.

According to the procedure for treatment of polluted water with ozone in the presence of a phenol, of benzoic acid or dodecylbenzenesulfonic acid, that in the unchecked Japanese patent publication No. 06-23377 is specified, it is difficult to get dirty water with ozone sufficiently with efficiency in the presence of the catalyst to treat.

epiphany the invention

According to the present invention, in a process for removing harmful materials, especially environmental hormones in water, by injecting ozone into the water Nonylphenol and / or a cresol added to the water to be treated according to claim 1.

Preferably the same Process the nonylphenol with a lower alcohol or Acetone added to the water to be treated.

Preferably the same Process the cresol together with a lower alcohol or acetone added to the water to be treated.

Preferably as the nonylphenol add a p-nonylphenol added.

Preferably as the cresol added p-cresol.

When the nonylphenol is added a nonylphenol with two molecular weights of 220 and 107 when measured using gas chromatography and / or mass spectrometry are used.

Brief description of the drawings

1 is a schematic that explains the radical formation reaction of ozone.

2 is a mass spectrum of a nonylphenol as a catalyst according to the present invention.

3 Fig. 3 is a diagram showing an experimental device used in the method of the present invention, and

4 is a table showing the test results of Example 1.

Best kind and Way of performing the invention

According to the present invention is the Addition of a catalyst containing a nonylphenol or cresol contains as the main component, for example 0.1 ppm by weight, although the optimal amount depends on the condition depends on the water to be treated.

That as a catalyst according to the present invention Nonylphenol is used during decomposed after treatment. It will probably turn into a phenol which is an alkyl group with a carbon number of almost 9 or not more than 9 is bound.

The nonylphenol as a catalyst can be an o-, an m- or a p-nonylphenol. The p-nonylphenol is preferred and it has been demonstrated that it has a high effect on the Accelerate the decomposition of organic materials with ozone Has.

The cresol as a catalyst can be an o-, an m- or a p-cresol. Of the three types of cresol, the p-cresol is the one that has the greatest effect on accelerating the decomposition of organic materials with ozone in the following example 2 had preferred.

Also, in a process according to the present Invention a lower alcohol or acetone together with the nonylphenol or added to the cresol as a catalyst for the water to be treated, so that the nonylphenol or the cresol are dissolved in the water can. Im later Example 1 to be discussed was methanol as the lower alcohol used. Im later Example 2 to be discussed was acetone. The type and The way of adding the nonylphenol or the cresol is not on limited the manner described above. Every way is possible, if they have the nonylphenol or cresol in the water to be treated makes soluble. Other solvents or wetting agents can be used become.

Furthermore, by adding a Wetting agent injected into the water to be treated Bubbles of ozone are kept so that the contact surfaces between the water and the Ozone increased can be. Therefore, the reaction speed can be increased.

Although the mechanism regarding the way the existing nonylphenol is applied to a reaction system of ozone according to the present Invention works, not elucidated , it is acceptable that the nonylphenol form hydroxyl radicals with a higher one oxidizing power accelerated from the ozone, causing the oxidative decomposition of organic Materials in water to be treated is accelerated.

With this in mind, the self-decomposition reaction of ozone in water, which in 1 is explained, an ozone molecule with a hydroxide ion such that the hydrogen superoxide or the superoxide ion is formed. Furthermore, the hydrogen superoxide formed reacts with an ozone molecule in such a way that oxygen and the hydroxyl radical are formed. As such, the hydroxyl radical formed decomposes the organic materials in water to be treated oxidatively, but the amount thereof is not so large that the organic materials would be decomposed sufficiently.

On the other hand, if a substance X capable of accelerating the self-decomposition of ozone is present in water, the hydroxyl radical further becomes from the ozone molecule through its contact with the substance X, as in 1 is formed, in addition to that formed as described above, whereby the hydroxyl radical formed is increased such that the decomposition of organic materials in the water to be treated is accelerated. It is suggested that the nonylphenol as the catalyst according to the present invention can function as substance X which can accelerate the self-decomposition of ozone, that is, as a reduction catalyst for ozone, or more specifically, the compounds formed in the decomposition process of the nonylphenol with ozone Accelerate self-decomposition of ozone and the oxidative decomposition of organic materials.

The nonylphenol used as the catalyst according to the present invention was determined by means of gas chromatography and mass Spectrometry analyzed, where there are two different peaks with molecular weights of 220 and 107, as in 2 indicated, showed. This suggests that the nonylphenol has a high purity without containing other substances and has the properties shown by gas chromatography and mass spectrometry.

With regard to this occurs when others commonly used nonylphenols too by injection of ozone too Treating water are given to accelerate the reaction of ozone not. The commonly used nonylphenols have been analyzed by gas chromatography and mass spectrometry. As The result showed several peaks. This demonstrated that the other commonly used nonylphenols mixed with other isomers are.

So it’s clear that a nonylphenol, at which two molecular weights of 220 and 107 when measured using Gas chromatography and / or mass spectrometry are recorded, preferred as a catalyst that accelerates the reaction of ozone is.

The catalyst, which is a nonylphenol or containing a cresol as the main component is called an AM catalyst designated.

The following are examples of the described the present invention. However, it is clear that the present invention is not limited to the examples.

EXAMPLE 1

River water samples I, N were obtained. The Concentrations of nonylphenol isomers as a phenol type substance in river water samples I, N and pure water were determined. After that, the river water samples obtained were I, N and the pure Put 500 ml of water in each container. A standard reagent (which is the aforementioned nonylphenol, which has two peaks the molecular weights 220 and 107 when measured by gas chromatography and / or has mass spectrometry and contains methanol) according to the present Invention was added and then ozone was injected. The Standard reagent was added in an amount of 100 μg, based on 1 liter of water. After that, the amounts of phenol-type substances in the Samples of extracted river water and pure water were included, determined. The above treatment was carried out at room temperature.

The concentration of substances of the phenol type contained in the river water sample I was 0.1 μg / l. That in the river water sample N was 5.1 μg / l and that in pure water was up to 0.1 μg / l.

For the river water sample I the injection amount of ozone was 8.5 g, the injection duration 40 min, the injection quantity of the gas 1 N1 / min and the absorption amount of ozone 3.9 g.

For the river water sample N the injection amount of ozone was 6.3 g, the injection duration 30 min, the injection quantity of the gas 1 N1 / min and the absorption amount of ozone is 3.3 g.

For the sample of pure water was the injection amount of ozone 6.0 g, the injection duration 30 min, the injection amount of the gas 1 N1 / min and the absorption amount of ozone 3.0 g.

After adding the standard reagent and injecting ozone, the amounts of the phenol type substance in the river water samples I, N and the pure water were determined. How out 4 can be seen, all measurements of substances of the phenol type in the river water samples I, N and the sample of pure water were up to 0.1 μg / l.

As can be seen from Example 1, the concentration of nonylphenols or nonylphenol isomers, the substances contained in the samples (especially samples I and N) of the phenol type and are problematic environmental hormones be considered, reduced.

Furthermore, the result that the proven concentration of substances of the phenol type in the pure water with which the aforementioned nonylphenol containing standard reagent was added and treated with ozone was 0.1 μg / l was clear that the added nonylphenol itself by the in Presence of the nonylphenol formed hydroxyl radicals and oxygen radicals is also oxidatively decomposed. In other words, accelerated the addition of the nonylphenol as the catalyst of the present invention the decomposition reaction of ozone and it interferes with the ozone or the hydroxyl radical caused oxidative decomposition reaction of Materials not.

EXAMPLE II

To 300 ml of super pure water 100 ml of tap water were added and one containing a wetting agent aqueous dripped red ink. The solution formed was placed in a 500 ml beaker 1 Form a solution A given. Air was injected into the prepared solution A. In this No foaming was caused in the case.

After that, as in 3 indicated ozone in the beaker 1 containing solution A through a line 2 with an ozone generator 3 injected. As a result, when ozone was injected, the phenomenon of foaming occurred in Solution A. The phenomenon of foam formation only lasted for about 5 minutes.

Thereafter, a drop (about 0.03 ml) of a solution of a nonylphenol dissolved in acetone in an amount such that a concentration of 10 µg / l was obtained was added to the solution A. After that, ozone was poured into the beaker 1 containing solution A to which the solution prepared by dissolving nonylphenol in acetone was set over a line 2 with the ozone generating device 3 injected. As a result, the phenomenon of foaming continued for 10 minutes or more.

Alternatively, solution A was used Drop (about 0.03 ml) acetone and ozone as in the previous described injected. As a result, the phenomenon of foaming occurred however, the foam disappeared 5 minutes later.

Alternatively, solution A was used Drops (approximately 0.03 ml) of reagents by dissolving such an amount of o-cresol, m-kersol and p-cresol, that a concentration of 10 μg / l obtained, prepared in acetone, added, and ozone injected as described above.

With regard to solution A, the o-cresol was added, the phenomenon of foaming continued.

With regard to solution A, the m-cresol was added, the phenomenon of foaming continued.

With regard to solution A, the p-cresol was added, the phenomenon of foaming continued and it became the phenomenon a strong one Foaming observed.

On the decomposing effect of the coloring substance serving red ink and wetting agent is the presence of residual chlorine (Cl) in tap water required. In case that Ozone is injected into water without chlorine, bubbles are white in color generated. The solution A comprised residual chlorine (Cl) that was present in the tap water, so colored by the red ink red blisters were formed when ozone was injected into them. If only ozone injected, the red vesicles disappeared as described above, soon. For in the event that ozone is in the solution A was injected after the addition of the nonylphenol or cresol, the phenomenon lasted the foam formation as described above, starting with red vesicle were formed and the vesicles then turned white. Because of these facts, it is suggested that the nonylphenol and the cresol the decomposition of disruptive coloring materials and wetting agents, those in the solution A are included, accelerated with ozone.

commercial applicability

As described above, accelerates according to the procedure In the present invention, the addition of a nonylphenol to the decomposition reaction of ozone, which makes it possible the oxidative decomposition reaction of organic materials accelerate through ozone. Therefore, the amount of ozone with the decomposition time, those for the decomposition of nonylphenols or nonylphenol isomers, the as estrogens considered harmful Phenol type substances are used in the treatment of waste water or Dirty water can be reduced to prevent pollution. Can too the cost of decomposing harmful materials, in particular Nonylphenols or nonylphenol isomers, the harmful substances considered as estrogens are of the phenol type so the harmful materials are converted into harmless ones are required to be reduced.

By adding a nonylphenol or a cresol to water, the phenol type organic materials contains and injecting ozone into this, there is a strong possibility that not only the organic materials but also the added ones Nonylphenol or cresol are decomposed and removed.

Furthermore, since the rate of decomposition of organic materials by ozone by adding a nonylphenol or a cresol according to the im the previously described method can be accelerated, water treatment using ozone if such Method used to speed up the reaction of ozone improved in terms of the rate of treatment of water that the treatment volume of the water to be treated increased per time can be, making the local area for treatment plants also for the case that the capacity of a reaction vessel is reduced is can be reduced. Furthermore, through this treatment the removal proportions of the substances of the phenol type and the nonylphenols or Nonylphenol isomers, which are problematic environmental hormones be considered, increased.

6. Procedure for accelerating the Reaction of ozone according to claim 5, characterized in that a p-cresol as the cresol is added for addition.

7. Procedure for accelerating the Reaction of ozone according to claim 5, characterized in that a lower alcohol or acetone to the water to be treated is given.

Claims (5)

Process for accelerating the reaction of ozone in the Treatment of water by injecting ozone into the water Removal of harmful Materials, smelling materials and colored materials, thereby characterized in that a cresol and / or a nonylphenol, wherein the nonylphenol has two molecular weights of 220 and 107, which at Measurement using gas chromatography and / or mass spectrometry are determined, added to the water to be treated. A method for accelerating the reaction of ozone according to claim 1, characterized net that the nonylphenol is used for the addition as a reduction catalyst for the ozone. A method for accelerating the reaction of ozone according to claim 1, characterized in that a p-nonylphenol as the nonylphenol for addition is added. A method for accelerating the reaction of ozone according to claim 1, characterized in that a lower alcohol or Acetone is added to the water to be treated. A method for accelerating the reaction of ozone according to claim 1, characterized in that a cresol to be treated Water is given.